Methods of removing contaminant impurities during the manufacture of a thin film transistor by applying water in which ozone is dissolved

ABSTRACT

The present invention is provided in order to remove contamination due to contaminant impurities of the interfaces of each film which forms a TFT, which is the major factor that reduces the reliability of TFTs. By connecting a washing chamber and a film formation chamber, film formation can be carried out without exposing TFTs to the air during the time from washing step to the film formation step and it becomes possible to maintain the cleanliness of the interfaces of each film which form the TFT.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a semiconductor device such as a thinfilm transistor (hereinafter referred to as TFT) which is formed on asubstrate using a crystalline semiconductor film as well as to amanufacturing method of the same. The semiconductor device of thepresent invention includes not only elements such as TFT and MOStransistor, but also a liquid crystal display device comprising asemiconductor circuit (micro-processor, signal processing circuit andhigh frequency circuit and the like) constructed of the aboveinsulation, gate type transistors, an EL (Electro Luminescence) displaydevice, an EC (Electro Chromic) display device and an image sensor andthe like.

2. Description of the Related Art

At present, as a semiconductor element using a semiconductor film, athin film transistor (hereinafter, referred to as TFT) is used in avariety of integrated circuits, in particular, as a switching element ofan image display device. In addition, a TFT using a crystallinesemiconductor film, of which the mobility is higher than that of anamorphous semiconductor film, as an active layer has a high drivingperformance and is used as an element of a driving circuit.

Reliability is seen as the most important factor in evaluating a TFT. Asfor a factor that decreases reliability, impurities in a TFT(hereinafter, impurities which lower the reliability of a TFT arereferred to as contaminant impurities in the present specification) arecited. These contaminant impurities become mixed into a TFT from avariety of contamination sources, such as an atmosphere, a glasssubstrate or a manufacturing device, etc. In particular, the existenceof contaminant impurities on the interfaces of a film forming a TFTbecomes a major factor that decreases the reliability of the TFT.

SUMMARY OF THE INVENTION

A semiconductor device is usually produced in a clean room. In a cleanroom, filters are used for removing dirt, dust, contaminants, or thelike from the outside air which is taken into the room. Contaminantimpurities generated from the filters themselves, particularly boron(B), or contaminant impurities from human beings working in the cleanroom, particularly sodium (Na), exist in large amounts in the clean roomatmosphere. That is to say, by merely exposing a substrate to theatmosphere of the clean room, the surface of the substrate getscontaminated.

Most of the steps of forming a variety of films which form a TFT,however, cannot be carried out in a sequential process. For example, acrystalline semiconductor film is obtained by using a method whichcrystallizes an amorphous semiconductor film with heat, laser light, orthe like. Crystallization of the amorphous semiconductor film withannealing becomes difficult in the case that an insulating film lies onthe amorphous semiconductor film and, therefore, the crystallization iscarried out under the condition where no insulating film exists on thesemiconductor film. Accordingly, it is necessary to wash the surface ofthe semiconductor film before the formation of the insulating film. Thatis to say, the step of washing the surface of the first film before theformation of the second film becomes necessary. During the time beforebeing put into a film formation unit from a washer, however, a substrateis exposed to the atmosphere.

The present invention is provided for maintaining the clean condition ofan interface of each film forming a TFT without being contaminated bycontaminant impurities.

In order to solve the above described problem, the present inventionprovides a washing chamber for removing contaminant impurities from thesurface of the first film with the film formation unit via aloader/unloader chamber, and is characterized by the sequentialprocessing from the removal of contaminant impurities from the surfaceof the first film, to the formation of the second film. In other words,the present invention is characterized in that, since the step ofwashing the surface of the first film and the step of forming the secondfilm are processed in sequence within one unit, the above steps areprocessed without exposure to the atmosphere including the intervalbetween them.

In the above described configuration, the removal of contaminantimpurities from the surface of the first film is carried out by etchingthe surface of the first film extremely thin using an acid solutionwhich includes fluorine, after carrying out the washing with pure waterin which ozone is dissolved. As for the means of etching extremely thin,there is an effective method of spinning the substrate using a spinningdevice so as to make the acid solution, which includes fluorine and isin contact with the surface of the first film, fly off in the air in alldirections.

The reasons why the above pure water, in which ozone is dissolved, isused are cited as follows:

(1) An extremely thin oxide film is formed on the surface of the firstfilm by means of ozone so that contaminant impurities adhered to thesurface of said first film can be removed together with said extremelythin oxide film by using the subsequent acid solution which includesfluorine.(2) In the case that the first film is hydrophobic, by oxidizing thesurface thereof with ozone, the surface of the first film is convertedto be hydrophilic so that the effects of washing increase.(3) A microscopic amount of a carbonized substance which may exist inthe clean room atmosphere can be removed through ozone oxidation and theresulting resolution.

As for the acid solution which includes fluorine, fluoric acid, dilutefluoric acid, ammonium fluoride, buffered fluoric acid (mixed solutionof fluoric acid and ammonium fluoride), a mixed solution of fluoric acidand hydrogen peroxide, or the like, can be used.

Accordingly, a semiconductor device of the present invention ischaracterized in that contaminant impurities of the surface of each filmforming a TFT are removed by providing a spinning type washer in thewashing chamber and by using pure water in which ozone is dissolved, andan acid solution containing fluorine, as a washing liquid.

In accordance with the present invention, contamination, due to contactwith air, of the interfaces of the films which form TFTs can beprevented and, therefore, dispersion of the characteristics of the TFTscan be reduced so that the reliability of the TFTs can be increased. Inaddition, the instability of the display of an EL display device, whichis greatly affected by the dispersion of the characteristics of the TFTsbecause of current drive, can be reduced.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a view of a film formation unit which includes a washer;

FIG. 2 is a cross section view of a TFT according to the example 1;

FIG. 3 is a cross section view of a TFT according to the example 1;

FIG. 4 is a cross section view of a TFT according to the example 1;

FIG. 5 is a top view of a pixel part of an active matrix substrateprocessed in the example 1;

FIG. 6 is a cross section view of a TFT according to the example 1;

FIG. 7 is a top view and a cross section view of an EL display panelaccording to the example 3;

FIG. 8 is a cross section view of an EL display panel according to theexample 3;

FIG. 9 is a top view of an EL display panel according to the example 3;

FIG. 10 is a view showing a variety of semiconductor devices accordingto the example 4:

FIG. 11 is a view showing a variety of semiconductor devices accordingto the example 4: and

FIG. 12 is a view showing a variety of semiconductor devices accordingto the example 4.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

An embodiment mode of the present invention is described in thefollowing with reference to FIG. 1. In addition, the present inventioncan, of course, be applied to a film formation unit wherein there is asingle film formation chamber or to a film formation unit wherein aplurality of film formation chambers are aligned along a line.

In FIG. 1, substrates set in a loader/unloader chamber 101 are carriedinto a washing chamber 110 one by one by a carrier robot 109 and thewashing process is performed. Substrates after the washing process arecarried by the carrier robot 109 into a loader/unloader chamber 103provided between the washing chamber and a film formation chamber. Whenit is completed to collect all of the substrates after completing thewashing process, the loader/unloader chamber 103 is vacuumed. Then, thesubstrates are carried into any of the film formation chambers 104 to107 by a carrier robot 108 and necessary films are formed. Substratesare collected in a loader/unloader chamber 102 after finishing the filmformations.

In the film formation chambers 104 to 107, gas exhaustion means 104 p to107 p and gas introduction means 104 g to 107 g are respectivelyprovided and the film formations of semiconductor films, insulatingfilms and conductive films are carried out.

Here, the washing chamber 110 is purged with N₂ so as to prevent themixing in of contaminants from the atmosphere.

In addition, the loader/unloader chamber 103 is vacuumed aftercompleting washing all of the processed substrates because the washingchamber is subject to atmospheric pressure while the film formationchamber is under the condition of reduced pressure.

Films in the present configuration indicate films formed by using avariety of formation means such as a plasma CVD method, a thermal CVDmethod, a reduced pressure CVD method, a vapor deposition method, asputtering method, a thermal oxidation method and a positive electrodeoxidation method.

In addition, contaminant impurities in the present configuration consistof one element, or a plurality of elements, existing in the atmosphere,and in particular, consist of one element or a plurality of elements,selected from among B, Na, K, Mg and Ca.

Although examples of the present invention are shown in the following,the present invention is not particularly limited to these.

EXAMPLES Example 1

Examples of the present invention are described with reference to FIGS.2 to 6. Here, a method for simultaneously manufacturing a pixel portionand TFTs (n channel type TFTs and p channel type TFTs) of a drivingcircuit provided around the periphery of the pixel portion on the samesubstrate is described in detail.

As for a substrate 200, a glass substrate, a quartz substrate, a ceramicsubstrate, or the like, can be used. In addition, a substrate obtainedby forming an insulating film on the surface of a silicon substrate, ametal substrate or a stainless substrate may be used. Moreover, aplastic substrate, which has sufficient heat resistance to withstand theprocessing temperature in the present example, may be used.

Next, as shown in FIG. 2A, a base film 201 made of an insulating film,such as a silicon oxide film, a silicon nitride film or a silicon oxidenitride film, is formed on the substrate 200. Though a double-layeredstructure is used for the base film 201 in the present example, a singlelayered film of said insulating film, or a structure where two or morelayers are laminated, may be used. As for the first layer of the basefilm 201, a silicon oxide nitride film 201 a of 50 nm to 100 nm, whichis formed by using a plasma CVD method with SiH₄, NH₃ and N₂O asreactive gases, is formed. Then, as for the second layer of the basefilm 201, a silicon oxide nitride film 201 b of the thickness of 100 nmto 150 nm, which is formed by using a plasma CVD method with SiH₄ andN₂O as reactive gases, is laminated.

Next, semiconductor layers 202 to 206 are formed on the base film. Afterthe formation of a semiconductor film with an amorphous structure by awell-known means (sputtering method, LPCVD method or plasma CVD method),the semiconductor layers 202 to 206 are formed by patterning thecrystalline semiconductor film, which is obtained by carrying out awell-known crystallization process (laser crystallization method,thermal crystallization method, thermal crystallization method using acatalyst such as nickel, or the like), into the desired form. Thissemiconductor layers, 202 to 206, are formed to have the thickness of 30nm to 60 nm. Though there are no particular limitations as to thematerials of the crystalline semiconductor film, it is, preferably,formed of silicon, silicon germanium alloy (SiGe), or the like.

In addition, since it is possible to form the base film 201 and theamorphous semiconductor film by the same film formation method, it isdesirable to form the base film 201 and the amorphous semiconductor filmin sequence. For example, in the film formation unit of FIG. 1, asubstrate is preheated in the heating chamber 104, the base film 201 ais formed in the first film formation chamber 105, then the base film201 b is formed in the second film formation chamber 106 and, finally,the film formation of the amorphous semiconductor film is carried out inthe third film formation chamber 107. As a result, impuritycontamination of the film interfaces can be prevented so as to reduceone factor that causes deterioration to the characteristics of the TFT.

In addition, after the formation of the semiconductor layer 202 to 206,doping of a microscopic amount of impurity elements (boron orphosphorous) may be carried out in order to control the threshold of theTFTs.

Next, the sequential process of the removal of the contaminantimpurities 207 which exist on the surface of the island-shapedsemiconductor layer 202 to 206, and the formation of a gate insulatingfilm 208 is carried out. Substrates are set in the loader/unloaderchamber 101 of the unit shown in FIG. 1 and are, one by one, subjectedto a spinning wash process in the washing chamber 110. Here, by usingpure water in which ozone is dissolved, and an acid solution containingfluorine, the contaminant impurities 207 can be removed together with anextremely thin oxide film formed in washing with pure water in whichozone is dissolved. As for preparation of the pure water in which ozoneis dissolved, there are methods of electrically resolving pure water, ofdirectly dissolving ozone gas into pure water, or the like. In addition,the water is utilized at, preferably, an ozone concentration of 6 mg/Lor more. Here, as for the number of revolution of the spinning device orthe time conditions, the optimal conditions may be properly setaccording to the substrate area, the film material, and the like. Aftercompletion of the washing process, substrates are collected in theloader/unloader chamber 103 which is provided between the washingchamber and the film formation chamber. When all of the substrates arecollected, the loader/unloader chamber 103 is vacuumed.

After that, the gate insulating film 208 is formed in the film formationchambers 104 to 107. The gate insulating film 208 is formed through aplasma CVD method or a sputtering method and is formed of an insulatingfilm which includes silicon, and the thickness thereof is made to be 40nm to 150 nm. After completing the film formation, the substrates arecollected in the loader/unloader chamber 102. The gate insulating filmis not limited to a silicon oxide nitride film and, a single layer or alayered structure, of another insulating film which includes silicon,may be used.

Next, the sequential process of the removal of contaminant impuritiesexisting on the surface of the gate insulating film 208 and of theformation of a gate conductive film is carried out. In the presentexample, a first conductive film (TaN) 209 of the film thickness of 20nm to 100 nm and a second conductive film (W) 210 of the film thicknessof 100 nm to 400 nm are laminated. The gate conductive films may beformed of an element selected from among Ta, W, Ti, Mo, Al, Cu or of analloy material, or a compound material, of which the major component isthe above element. In addition, a semiconductor film represented by apolycrystal silicon film, into which impurity elements such asphosphorous are doped, may be used. Moreover, a combination wherein thefirst conductive film is formed of a Ta film and the second conductivefilm is made of a W film, a combination wherein the first conductivefilm is formed of a TaN film and the second conductive film is formed ofan Al film, or a combination wherein the first conductive film is formedof a TaN film and the second conductive film is made of a Cu film, maybe used.

Here, in the case that the sequential formations of the gate insulatingfilm 208 and the gate conductive films 209 and 210 are carried out, theabove described washing step can be omitted.

Next, masks 211 to 216 made of resist is formed by using aphotolithographic method and the first etching process is carried outfor forming electrodes and wirings. In the present example an ICP(inductively coupled plasma) etching method is used and CF₄, Cl₂ and O₂are used as gases for etching so that the gas flow ratio of respectivegases is made to be 25/25/10 (scan) and, then, the etching is carriedout by applying an RF (13.56 MHz) power of 500 W to a coil typeelectrode under the pressure of 1 Pa so as to generate plasma. An RF(13.56 MHz) power of 150 W is applied to the substrate side (samplestage) so that a substantially negative self-biasing voltage is applied.The W film is etched under this first etching condition so that theedges of the first conductive layer become of a tapered form.

Thereafter, the etching condition is converted to the second etchingcondition without removing the mask 211 to 216 made of the resist, CF₄and Cl₂ are used as the gases for etching so that the gas flow ratio ofrespective gases is made to be 30/30 (scan) and, then, an RF (13.56 MHz)power of 500 W is applied to a coil type electrode under the pressure of1 Pa so as to generate plasma and etching is carried out forapproximately 30 seconds. An RF (13.56 MHz) power of 20 W is applied tothe substrate side (sample stage) so that a substantially negativeself-biasing voltage is applied. Under the second etching conditionwherein CF₄ and Cl₂ are mixed, the W film and the TaN film are etched tothe same degree. Here, in order to carry out the etching without leavinga residue on the gate insulating film, the etching time may be increasedby the ratio of approximately 10% to 20%.

In the above described first etching process, by making the form of themasks made of the resist suitable, the edges of the first conductivelayer and the second conductive layer become of a tapered form due tothe effect of the biased voltage applied to the substrate side. Theangle of these tapered portions becomes 15° to 45°. Thus, the conductivelayers 218 to 223 in a first form made of the first conductive layer andthe second conductive layer (first conductive layer 218 a to 223 a andsecond conductive layer 218 b to 223 b) are formed through the firstetching process. The gate insulating film is denoted as 217 and theregions which are not covered with the conductive layer 218 to 223 inthe first form are etched by approximately 20 nm to 50 nm so thatthinner regions are formed.

Then, the first doping process is carried out without removing the masksmade of the resist so that impurity elements are added to thesemiconductor layer (FIG. 2(C)), which is converted to the n type. Asfor the doping process, an ion doping method or an ion injection methodmay be carried out. As for the conditions of the ion doping method, thedosage is 1×10¹³ atoms/cm² to 5×10¹⁵ atoms/cm² and acceleration voltageis 60 keV to 100 keV. As for the impurity elements which convert thesemiconductor layer into the n type, elements which belong to group 15,typically phosphorous (P) or arsenic (As), are used. In this case, theconductive layers 218 to 222 work as masks against the impurityelements, which convert the semiconductor layer into the n type, so thatthe first impurity regions 224 to 228 are formed in a self-alignedmanner. The impurity elements which convert the semiconductor layer intothe n type are added in the concentration ranging from 1×10²⁰ atoms/cm³to 1×10²¹ atoms/cm³ into the first impurity regions 224 to 228.

Next, the second etching process is carried out without removing themasks made of the resist as shown in FIG. 3A. The second etching processis carried out under the third and the fourth etching conditions. As forthe third etching condition, an ICP etching method is used in the samemanner, wherein CF₄ and Cl₂ are used as the etching gases so that thegas flow ratio of the respective gases is made to be 30/30 (sccm), an RFpower (13.56 MHz) of 500 W is supplied to the coil type electrode underthe pressure of 1 Pa so as to generate plasma, and the etching iscarried out for approximately 60 seconds. An RF (13.56 MHz) power of 20W is given to the substrate side (sample stage) so that a self-biasingvoltage which is lower than that in the first etching process isapplied. Under the third etching condition in which CF₄ and Cl₂ aremixed, the W film and the TaN film are etched to the same degree.

Thereafter, the etching condition is converted to the fourth etchingcondition without removing the masks made of the resist, in which CF₄,Cl₂ and O₂ are used for the gases for the etching so that the gas flowratio of the respective gases is made to be 25/25/10 (sccm), an RF(13.56 MHz) power of 500 W is applied to the coil type electrode underthe pressure of 1 Pa so as to generate plasma, and the etching iscarried out for approximately 20 seconds. An RF (13.56 MHz) power of 20W is given to the substrate side (sample stage) so that a self-biasingvoltage which is lower than that in the first etching process isapplied. Under this fourth etching condition, the W film is etched.

Thus, the W film is etched in an anisotropic manner under the abovedescribed third and fourth etching conditions and the TaN film is etchedin an anisotropic manner with a slower etching rate than that of the Wfilm so as to the conductive layers 230 to 235 in the second form (firstconductive layer 230 a to 235 a and second conductive layer 230 b to 235b). The gate insulating film is denoted as 229 and the regions which arenot covered with the conductive layer 230 to 235 in the second fatal areetched to become thinner by the film thickness of approximately 10 nm to20 nm.

The etching reaction with the mixed gas of CF₄ and Cl₂ to the W film orthe TaN film can be estimated from types of generated radicals or ionsand vapor pressure of products after the reaction. Comparing the vaporpressures of the fluorides and chlorides of W and TaN, WF₆, which is afluoride of W, is extremely high and the others, WCl₅, TaF₅ and TaCl₅,are approximately the same. Accordingly, both the W film and the TaNfilm are etched with the mixed gas of CF₄ and Cl₂. When a proper amountof O₂ is added to this mixed gas, however, CF₄ and O₂ react to become COand F so as to generate a large amount of F radicals or F ions. As aresult, the etching rate of the W film increases since vapor pressure ofthe fluoride is high. On the other hand, the increase of the etchingrate for TaN is comparatively small even when F increases. In addition,TaN can be more easily oxidized compared to W and, therefore, theaddition of O₂ causes a slight oxidization of the surface of TaN. Sincethe oxides of TaN do not react with fluorine or chlorine, the etchingrate of the TaN film is further reduced. Accordingly, it becomespossible to make a difference between the etching rates of the W filmand the TaN film and it becomes possible to make the etching rate of theW film be greater than that of the TaN film.

Next, the second doping process is carried out without removing themasks made of the resist as shown in FIG. 3B. In this case, impurityelements which convert the semiconductor layer into the n type are dopedunder the condition of a high acceleration voltage with making thedosage lower than in the first doping process. For example, theacceleration voltage is 70 keV to 120 keV. In the present example theacceleration voltage is 90 keV and the dosage is 3.5×10¹² atoms/cm² soas to form new impurity regions in the semiconductor layer inside of thefirst impurity regions formed in FIG. 2C. As for the doping, theconductive layers 230 to 234 in the second form are used as masksagainst the impurity elements and the doping is carried out so thatimpurity elements are added to the semiconductor layer beneath thetapered portions of the second conductive layers 230 a to 234 a.

Thus, the third impurity regions 241 to 245 which overlap the secondconductive layers 230 a to 234 a, and the second impurity regions 236 to240 between the first impurity regions 246 to 250 and the third impurityregions 241 to 245, are formed. The impurity elements which convert thesemiconductor layer to the n type are made to have the concentration of1×10¹⁷ atoms/cm³ to 1×10¹⁹ atoms/cm³ in the second impurity regions andthe concentration of 1×10¹⁶ atoms/cm³ to 1×10¹⁸ atoms/cm³ in the thirdimpurity regions. Here, in the third impurity regions 241 to 245, theconcentration of the impurity elements which convert the semiconductorlayer to the n type and is included at least in the parts which overlapthe conductive layers 230 a to 234 a in the second form, varies. That isto say, the concentration of phosphorous (P) added to the third impurityregions 241 to 245 gradually becomes lower toward the inside from theedge of the conductive layer in the regions which overlap the conductivelayers in the second form. This is because the concentration ofphosphorous (P) which reaches into the semiconductor layer varies inaccordance with the differences of the film thickness of the taperedparts.

Then, after removing the masks made of the resist, masks 251 to 253 madeof resist is newly formed so that the third doping process is carriedout as shown in FIG. 3C. Through this third doping process, the fourthimpurity regions 254 to 259 are formed, in which impurity elements whichconvert the semiconductor layer to p-type are added to the portion tobecome the active layer of the p channel type TFTs. By using theconductive layers 231 and 234 in the second form as masks againstimpurity elements, impurity elements which convert the semiconductorlayer into the p type are added so that the fourth impurity regions areformed in a self-aligning manner. In the present example the impurityregions 254 to 259 are formed with an ion doping method using diborane(B₂H₆). In this third doping process, the semiconductor layer formingthe n channel type TFTs is covered with the masks 251 to 253 made of theresist. Though phosphorous is added in the impurity regions 254 to 259in respectively different concentrations in the first doping process andthe second doping process, the third doping process is carried out sothat the concentration of the impurity elements, which convert thesemiconductor layer to the p type, becomes 2×10²⁰ atoms/cm³ to 2×10²¹atoms/cm³ in any of the regions, and there is no problem to function assource and drain regions of the p channel type TFTs.

With the above described processes, impurity regions are formed inrespective semiconductor layers. The conductive layers 230 to 234 in thesecond form, which overlaps the semiconductor layer, function as gateelectrodes. In addition, 235 functions as a source wiring while 234functions as the second electrode for forming a capacitance which holdsa charge.

Next, the masks 251 to 253 made of the resist are removed and the firstinterlayer insulating film 260, which covers the entire surface, isformed. The first interlayer insulating film 260 is formed of aninsulating film with the thickness of 100 nm to 200 nm, which includessilicon, by using a plasma CVD method or a sputtering method. In thepresent example, a silicon oxide nitride film with the film thickness of150 nm is formed through a plasma CVD method. The first interlayerinsulating film 260 is not, of course, limited to a silicon oxidenitride film and, a single layer of, or a laminate structure of anotherinsulating film which includes silicon, may be used.

Next, as shown in FIG. 4A, an activation process of impurity elementswhich are added to the respective semiconductor layers is carried out.This activation step is carried out through a thermal annealing methodwith an annealing furnace. The thermal annealing method is carried outat 400° C. to 700° C., preferably at 500° C. to 550° C. in a nitrogenatmosphere wherein the oxygen concentration is 1 ppm, or less,preferably 0.1 ppm, or less. Here, in addition to thermal annealingmethod, a laser annealing method or a rapid thermal annealing method(RTA method) can be applied.

In addition, before the formation of the first interlayer insulatingfilm 260, the activation process may be carried out. However, in thecase that the materials of the wirings used for 230 to 235 are easilyaffected by heat, it is preferable to carry out the activation processafter the formation of an interlayer insulating film (an insulating filmin which the main component is silicon, for example, a silicon nitridefilm) in order to protect the wirings, or the like, as in the presentexample.

In addition, the step of hydrogenating the semiconductor layer iscarried out in an atmosphere including 3% to 100% of hydrogen with heatprocessing of 1 hour to 12 hours at 300° C. to 550° C. This step is thestep of terminating the dangling bonds of the semiconductor layer withthermally-excited hydrogen. As for another means for hydrogenation, aplasma hydrogenation (using hydrogen excited by plasma) may be carriedout.

In addition, in the case that a laser annealing method is used for theactivation process, it is preferable to irradiate laser light such anexcimer laser or from a YAG laser, after carrying out the abovedescribed hydrogenation.

Next, the second interlayer insulating film 261, made of an organicinsulating material, is formed on the first interlayer insulating film260. Next, patterning is carried out for forming a contact hole whichreaches to the source wiring 235 and contact holes which reach to therespective impurity regions 246, 248, 249, 254 and 257.

Then, in the driving circuit 406, wirings 262 to 267 are formed to beelectrically connected to the first impurity regions or to the fourthimpurity regions, respectively. Here, these wirings are formed bypatterning a lamination film of a Ti film with the film thickness of 50nm and an alloy film (alloy film of Al and Ti) with the film thicknessof 500 nm.

In addition, in the pixel part 407, a pixel electrode 270, a gate wiring269 and a connection electrode 268 are formed (FIG. 4B). This connectionelectrode 268 forms an electric connection of the source wiring 235 tothe pixel TFT 404. In addition, the gate wiring 269 forms an electricconnection with the first electrode (conductive layer 233 in the secondform). In addition, the pixel electrode 270 forms an electric connectionwith the drain region of a pixel TFT and, moreover, forms an electricconnection with a semiconductor layer which functions as one electrodeof a capacitance. In addition, as the pixel electrode 270, it ispreferable to use a material with an excellent reflectivity such as afilm including Al or Ag as the major component, or a lamination filmcomposed of such films.

As the above, the driving circuit 406 which comprises an n channel typeTFT 401, a p channel type TFT 402 and an n channel TFT 403, and a pixelportion 407 which comprises a pixel TFT and a capacitance 405 can beformed on the same substrate. In the present specification, such asubstrate is referred to, for the purpose of convenience, as an activematrix substrate.

The n channel type TFT 401 in the driving circuit 406 contains a channelformation region 271; the third impurity region 241 (GOLD region) whichoverlaps the conductive layer 230 in the second form, which forms a gateelectrode; the second impurity region 236 (LDD region) which is formedoutside of the gate electrode; and the first impurity region 246 whichfunctions as a source region or a drain region. The p channel type TFT402 contains a channel formation region 272; the fourth impurity region256 which overlaps the conductive layer 231 in the second form, whichforms a gate electrode; the fourth impurity region 255 which is formedoutside of the gate electrode; and the fourth impurity region 254 whichfunctions as a source region or a drain region. The n channel type TFT403 contains the channel formation region 273; the third impurity region243 (GOLD region) which overlaps the conductive layer 232 in the secondform, which forms a gate electrode; the second impurity region 238 (LDDregion) which is formed outside of the gate electrode; and the firstimpurity region 248 which functions as a source or drain region.

The pixel TFT 404 in the pixel part contains the channel formationregion 274; the third impurity region 244 (GOLD region) which overlapsthe conductive layer 233 in the second form, which forms a gateelectrode; the second impurity region 239 (LDD region) which is formedoutside of the gate electrode; and the first impurity region 249 whichfunctions as a source region or as a drain region. In addition, in thesemiconductor layer 257 to 259 which functions as one of the electrodesof the capacitance 405, impurity elements which convert thesemiconductor layer into the p type are added with the sameconcentration as that of the fourth impurity regions. The capacitance405 is formed of the second electrode 234 and the semiconductor layer257 to 259 with the insulating film (same film as the gate insulatingfilm) as the dielectric.

A top view of the pixel portion of the active matrix substrate producedin the present example is shown in FIG. 5. Here, the parts correspondingto those in FIGS. 2 to 6 are referred to by the same numerals. The chainline A-A′ in FIG. 4 corresponds to the cross section view along thechain line A-A′ in FIG. 5. In addition, the chain line B-B′ in FIG. 4corresponds to a cross section view along the chain line B-B′ in FIG. 5.

Thus, the active matrix substrate with a pixel structure of the presentexample is characterized in that the first electrode 233, whichpartially functions as a gate electrode, and the gate wiring 269 areformed in different layers and the gate wiring 269 blocks light fromreaching the semiconductor layer.

In addition, the pixel structure of the present example is formed andarranged so that an edge part of a pixel electrode overlaps the sourcewiring in order to block light from reaching a gap between the pixelelectrodes without using a black matrix.

In addition, it is preferable to increase the whiteness by making thesurface of the pixel electrodes in the present example uneven through aknown method, for example, through a sand blast method or through anetching method, so as to prevent a mirror reflection and to scatter thereflected light.

By introducing the above described pixel structure, pixel electrodeswhich have large areas can be arranged so that the aperture ratio can beincreased.

In addition, in accordance with the steps shown in the present example,the number of photo masks, which is necessary for manufacturing theactive matrix substrate, can be made to be 5 (the pattern mask for thesemiconductor layer, the pattern mask for the first wiring (includingthe first electrode 233, the second electrode 234 and the source wiring235), the pattern mask for forming the source region and the drainregion of the p type TFT, the pattern mask for forming the contact holesand the pattern mask for the second wiring (including the pixelelectrode 270, the connection electrode 268 and the gate wiring 269)).As a result, the process can be shortened, which can contribute to thereduction of the manufacturing cost and to the increase of the yield.

An active matrix liquid crystal display device manufactured from theactive matrix substrate shown in FIG. 4B is shown in FIG. 6. After apillar-shaped spacer 572 of organic resin such as acryl resin is formed,an orientation film 567 is formed on the active matrix substrate andrubbing is performed. A spherical spacer may be used instead of thepillar-shaped spacer 572.

Next, An opposing substrate is prepared. Coloring layers 570 and 571,which may be a red coloring layer and a blue coloring layerrespectively, a leveling film 573, and an opposing electrode 576 areformed in order on the opposing substrate 569, and then an orientationfilm 574 is faulted over the entire surface of the opposing electrodefollowed by rubbing.

Then, the active matrix substrate and the opposing substrate are bondedwith a sealing material 568. A filler is mixed into the sealing material568, and the filler and pillar-shaped spacer 572 make the interval oftwo substrates keep uniform. A known material is used as liquid crystal575.

Example 2

In the case that the sequential process of forming the base film 201 andthe amorphous semiconductor film is not carried out in the example 1,the present invention can be used.

In accordance with the same manner as in the example 1, the base film201 is formed. Next, a sequential process of removal of contaminantimpurities which exist on the surface of the base film 201 and formationof an amorphous semiconductor film is carried out. The method forremoving the contaminant impurities on the surface of the base film andthe process following the formation of the amorphous may be carried outin the same manner as in the example 1.

Example 3

In Example 3, an example in which an EL (Electro Luminescence) displaydevice is manufactured by using an active matrix substrate formed inExamples 1 and 2, will be described. The EL display device is alsocalled a light emitting device or a light emitting diode, and aluminescent material put between electrodes, by which EL (ElectroLuminescence) can be obtained, includes all of materials which emitlight (phosphorescence and/or fluorescence) through singlet excitation,triplet excitation, or both. FIG. 7A is a top view of the EL displaypanel. In FIG. 7A, reference numeral 10 denotes a substrate, 11 denotesa pixel portion, 12 denotes a source-side driving circuit, and 13denotes a gate-side driving circuit. Each driving circuit is connectedto an FPC 17 through wirings 14 to 16 so as to be connected to anexternal equipment.

FIG. 7B shows a cross sectional view taken along the line A-A′ of FIG.7A. The counter substrate 80 is provided at least on the pixel portion,preferably on the driving circuits and the pixel portion. The countersubstrate 80 is attached to the active matrix substrate, on which TFTsand a self-emitting layer using an EL material are formed with a sealingmaterial 19. The sealing material 19 is mixed with a filler (not shownin the figure), two substrates are attached together with the filler atequal spaces. Further, the outside of the sealing material 19 and thetop surface and the periphery of the FPC 17 have a structure of beingfilled up by a sealant 81. As a material of the sealant 81, siliconeresin, epoxy resin, phenol resin and butyl rubber are used.

As it is, the active matrix substrate 10 and the counter substrate 80are attached together with the sealing material 19, space is generatedtherebetween. A filler 83 is filled with the space. The filler 83 has aneffect of attachment of the counter substrate 80. The PVC (polyvinylchloride), epoxy resin, silicone resin, or EVA (ethylene vinyl acetate)can be used as the filler 83. The self-emitting layer is weak tomoisture such as water and is likely to be degraded, so that it ispreferable to mix a drying agent such as barium oxide in the filler 83so as to keep an effect of moisture absorption. Further; a passivationfilm 82 is formed on the self-emitting layer by the silicon nitride filmand silicon oxynitride film to protect from corrosion by alkali elementor the like which contains in the filler 83.

In FIG. 7B, a driving circuit TFT 22 (CMOS circuit which is composed ofn-channel type TFT and p-channel type TFT is shown here), and a pixelportion TFT 23 (only a TFT for controlling a current flown to an ELelement is shown here) are formed on a substrate 10 and a base film 21.

To manufacture the EL display device from an active matrix substrateformed in the examples 1 and 2, an interlayer insulating film (aflattening film) 26 made of a resin material, is formed on the sourcewiring and the drain wiring, and a pixel electrode 27 made of atransparent conductive film, which is connected electrically to drain ofthe pixel portion TFT 23, is formed thereon. As a transparent conductivefilm, a compound of indium oxide and tin oxide (which is called as ITO),and a compound of indium oxide and zinc oxide can be used. After formingthe pixel electrode 27, an insulating film 28 is formed, and an openingportion is formed on the pixel electrode 27.

Next, a self-emitting layer 29 is formed. The self-emitting layer 29 mayhave a lamination structure which is obtained by freely combination withlayers made of known EL materials (hole injection layer, holetransporting layer, light-emitting layer, electron transportation layer,or electron injection layer) or a single structure. Such a structure canbe obtained by a known technique. Furthermore, examples of the ELmaterial include a low molecular-weight material and polymer material.In the case of using a low molecular-weight material, vapor depositionis used. In the case of using a polymer material, a simple method suchas spin coating, printing, and an ink jet method can be used.

The self-emitting layer is formed by vapor deposition, ink jet method ordispenser method using a shadow mask. In any way, by forminglight-emitting layers (red light-emitting layer, green-light emittinglayer, and blue light-emitting layer) capable of emitting light withdifferent wavelengths on respective pixels, a color display can beperformed. In addition, a combination of a color conversion layer (CCM)and a color filter, or a combination of a white light-emitting layer anda color filter may be used. Needless to say, an EL display deviceemitting single color light can also be used.

When the self-emitting layer 29 is formed, a cathode 30 is formedthereon. It is desirable to remove moisture and oxygen present at aninterface between the cathode 30 and the self-emitting layer 29 as muchas possible. Thus, it is required to continuously form the self-emittinglayer 29 and the cathode 30 in a vacuum, or to form the self-emittinglayer 29 in an inactive atmosphere, and form the cathode 30 in a vacuumwithout exposing to the outside air. In the present example, a filmformation device of a multi-chamber system (cluster tool system) is usedto make the above mentioned film formation possible.

The cathode 30 is connected to the wiring 16 in a region denoted byreference numeral 31. The wiring 16 is a power supply line for supplyinga predetermined voltage to the cathode 30, and is connected to the FPC17 via anisotropic conductive paste material 32. The sealant 81 isfurther formed on the FPC 17 so as to enhance adhesiveness in thisportion.

To electrically connect the cathode 30 with the wiring 16 in the region31, it is required to form contact holes in the interlayer insulatingfilm 26 and the insulating film 28. The contact holes may be formedduring etching of the interlayer insulating film 26 (during formation ofa contact hole for a pixel electrode) or during etching of theinsulating film 28 (during formation of an opening portion beforeforming the self-emitting layer). Furthermore, when the insulating film28 is etched, the interlayer insulating film 26 may also be etchedtogether. In this case, if the interlayer insulating film 26 and theinsulating film 28 are made of the same resin material, the shape of thecontact holes can be made fine.

Furthermore, the wiring 16 is electrically connected to the FPC 17through a gap between the sealing material 19 and the substrate 10 (thegap is filled with a sealant 81). Herein, although description is madewith respect to the wiring 16, other wirings 14 and 15 are alsoelectrically connected to the FPC 17 under the sealing material 19.

FIG. 8 shows a more detailed cross-sectional structure of the pixelportion and FIG. 9 shows a top view thereof. In FIG. 8A, a switching TFT2402 provided on a substrate 2401 is formed as the pixel TFT 404 shownin FIG. 4B of the example 1. In the present example, the TFT has adouble-gate structure, however, it may have a triple gate structure, ora multi-gate structure having more gates.

Further, the current controlling TFT 2403 has a structure in which anLDD overlapping with a gate electrode is provided at only drain side,and the structure has an ability of driving a current by reducing aparasitic capacitance and series resistance between a gate and drain.Further, since the current controlling TFT is an element for controllingthe amount of a current flowing through an EL element, the currentcontrolling TFT is likely to be degraded by heat and hot carriers due toa large amount of current flowed therethrough. Therefore, an LDD regionoverlapping partly with a gate electrode, is provided on the currentcontrolling TFT, thereby preventing the deterioration of TFT andenhancing the stability of the operation. At this time, a drain wiring35 of the switching TFT 2402 is electrically connected to the gateelectrode 37 of the current controlling TFT through the wiring 36.Further, the wiring denoted by a reference numeral 38 is a gate wiringfor connecting the gate electrodes 39 a and 39 b of the switching TFT2402.

Furthermore, in the present example, the current controlling TFT 2402has a single gate structure. However, it may have a multi-gate structurein which a plurality of TFTs are connected in series. Furthermore, itmay also be possible that a plurality of TFTs are connected in parallelto substantially divide a channel formation region into a plurality ofparts, so as to conduct highly efficient heat release. Such a structureis effective for preventing degradation due to heat.

As shown in FIG. 9, a wiring to be the gate electrode 37 of the currentcontrolling TFT 2403 overlaps a source wiring 40 of the currentcontrolling TFT 2403 via an insulating film in a region 2404. In theregion 2404, a capacitor is formed. The capacitor 2404 functions forholding a voltage applied to a gate of the current controlling TFT 2403.The source wiring 40 is connected to a current supply line (power sourceline) 2501 so as to be always supplied with a constant voltage.

A first passivation film 41 is provided on the switching TFT 2402 andthe current controlling TFT 2403, and a flattening film 42 that is madeof a resin insulating film is formed thereon. It is very important toflatten the step difference due to TFTs by using the flattening film 42.The step difference may cause a light-emitting defect because theself-emitting layer to be formed later is very thin.

Reference numeral 43 denotes a pixel electrode (cathode of an ELelement) that is made of a conductive film with high reflectivity and iselectrically connected to the drain of the current controlling TFT 2403.As the pixel electrode 43, a low resistant conductive film such as analuminum alloy film, a copper alloy film, and a silver alloy film, or alamination film thereof can be preferably used. Needless to say, alamination structure with other conductive films may also be used. Alight-emitting layer 45 is formed in a groove (corresponding to a pixel)formed by banks 44 a and 44 b made of an insulating film (preferablyresin). Herein, only one pixel is shown, however, light-emitting layerscorresponding to each color R (red), G (green), and B (blue) may beformed. As an organic EL material for the light-emitting layer, aπ-conjugate polymer material such as polyparaphenylene vinylene (PPV),polyvinyl carbazole (PVK), and polyfluorene is used.

In the present example, a self-emitting layer with a laminationstructure is used, in which a hole injection layer 46 made of PEDOT(polythiophene) or PAni (polyaniline) is provided on the light-emittinglayer 45. An anode 47 made of a transparent conductive film is providedon the hole injection layer 46. In the present example, light generatedby the light-emitting layer 45 is irradiated to the upper surface(toward the upper of TFTs), so that the anode must be transparent tolight. As a transparent conductive film, a compound of indium oxide andtin oxide, and a compound of indium oxide and zinc oxide can be used.The conductive film is formed after forming the light-emitting layer andthe hole injection layer with low heat resistance, so that theconductive film that can be formed at a possibly low temperature ispreferably used.

In the present example, referring to FIG. 8B, the case will be describedwhere the structure of the self-emitting layer is reversed. The currentcontrol TFT 2601 is formed as a p-channel type TFT 402 of FIG. 4. Themanufacturing process is referred to the example 1. In the presentexample, a transparent conductive film is used as a pixel electrode(anode) 50.

After banks 51 a and 51 b made of an insulating film are formed, alight-emitting layer 52 made of polyvinyl carbazole is formed by coatingof a solution. On the light-emitting layer 52, an electron injectionlayer 53 made of potassium acetyl acetonate (acacK), and a cathode 54made of an aluminum alloy are formed. In this case, the cathode 54functions as a passivation film. Thus, an EL element 2602 is formed. Inthe present example, light generated by the light-emitting layer 53 isirradiated toward the substrate on which a TFT is formed as representedby an arrow. In the case of the structure of the present example, it ispreferable that the current controlling TFT 2601 is formed of ap-channel TFT.

Example 4

A TFT formed by implementing the present invention is utilized forvarious display devices (typically, active matrix liquid crystaldisplay). Namely, the present invention can be applied to all ofelectronic equipments incorporating the electro-optical device or asemiconductor circuit as components

The following can be given as examples of such electronic equipments: avideo camera; a digital camera; a projector (rear type or front type); ahead mounted display (a goggle type display); a car navigation system; acar audio system; a personal computer; a portable information terminal(such as a mobile computer, a mobile telephone, or an electronic book).Examples of those electronic equipments are shown in FIGS. 10, 11 and12.

FIG. 10A illustrates a personal computer which includes a main body1001, an image input portion 1002, a display portion 1003, a key board1004, or the like. The present invention can be applied to the imageinput portion 1002, the display portion 1003, and other signalcontrolling circuits.

FIG. 10B illustrates a video camera which includes a main body 1005, adisplay portion 1006, an audio input portion 1007, operation switches1008, a battery 1009, an image receiving portion 1010, or the like. Thepresent invention can be applied to the display portion 1006, and othersignal controlling circuits.

FIG. 10C illustrates a mobile computer which includes a main body 1011,a camera section 1012, an image receiving section 1013, operationswitches 1014, a display portion 1015, or the like. The presentinvention can be applied to the display portion 1015, and other signalcontrolling circuits.

FIG. 10D illustrates a goggle type display which includes a main body1016, a display portion 1017, and an aim section 1018. The presentinvention can be applied to the display portion 1017, and other signalcontrolling circuits.

FIG. 10E illustrates a player using a recording medium which records aprogram (hereinafter referred to as a recording medium) and includes amain body 1019, a display portion 1020, a speaker section 1021, arecording medium 1022, and operation switches 1023. This player uses DVD(digital versatile disc), CD, etc. for the recording medium, and can beused for music appreciation, film appreciation, games and Internet. Thepresent invention can be applied to the display portion 1020 and othersignal controlling circuits.

FIG. 10F illustrates a digital camera which includes a main body 1024, adisplay portion 1025, a view finder portion 1026, operation switches1027, and an image receiving section (not shown in the figure). Thepresent invention can be applied to the display portion 1025 and othersignal controlling circuits.

FIG. 11A illustrates a front type projector which includes a projectingapparatus 1101 and a screen 1102. The present invention can be appliedto a liquid crystal display device 1114 which structures a portion ofthe projecting apparatus 1101, and other signal controlling circuits.

FIG. 11B illustrates a rear type projector which includes such a mainbody 1103, a projecting apparatus 1104, a mirror 1105, and a screen1106. The present invention can be applied to the liquid crystal displaydevice 1114 which, structures a portion of the projecting apparatus1104, and other signal controlling circuits.

Note that an example of the structure of the projecting apparatuses 1101and 1104 of FIG. 11A and FIG. 11B is shown in FIG. 11C. The projectingapparatuses 1101 and 1104 are composed of a light source optical system1107, mirrors 1108 and 1110 to 1112, a dichroic mirror 1109, a prism1117, the liquid crystal display device 1114, a phase difference plate1115, and a projecting optical system 1116. The projecting opticalsystem 1116 is composed of an optical system including a projectionlens. A three-plate type example is shown in the example 4, but thereare no particular limitations, and a single-plate type may also be used,for example. Further, optical systems such as an optical lens, a filmhaving a light polarizing function, a film for regulating the phase, andan IR film may be suitably placed in the optical path shown by the arrowin FIG. 11C by an operator.

Further, FIG. 11D is a diagram showing one example of the light sourceoptical system 1107 in FIG. 11C. In the example 4, the light sourceoptical system 1107 is composed of a reflector 1118, a light source1119, lens arrays 1120 and 1121, a polarizing transformation element1122, and a condenser lens 1123. Note that the light source opticalsystem shown in FIG. 11D is one example, and the light source opticalsystem is not limited to the structure shown in the figure. For example,optical systems such as an optical lens, a film having a lightpolarizing function, a film for regulating the phase, and an IR film maybe suitably added by the operator.

Note that a case using a transmitting type display device in theprojectors shown in FIG. 11 is shown here, and an example of applying areflecting type display device is not shown in the figures.

FIG. 12A illustrates a portable telephone, which includes a main body1201, an audio output portion 1202, an audio input portion 1203, adisplay portion 1204, operation switches 1205, and an antenna 1206. Thepresent invention can be applied to the audio, output portion 1202, theaudio input portion 1203, the display portion 1204, and other signalcontrolling circuits.

FIG. 12B illustrates a portable book (electronic book) which includes amain body 1207, a display portion 1208, a recording medium 1209,operation switches, 1210, and an antenna 1211. The present invention canbe applied to the display portions 1208, the recording medium 1209, andother signal controlling circuits.

FIG. 12C illustrates a display, which includes a main body 1212, asupport stand 1213, and a display portion 1214. The present inventioncan be applied to the display portion 1214. The display of the presentinvention is advantageous for cases of large size screens in particular,and is advantageous for displays having a diagonal equal to or greaterthan 10 inches (in particular, equal to or greater than 30 inches).

The applicable scope of the present invention is thus extremely wide, sothat the present invention can be applied to electronic equipments inall fields.

What is claimed is:
 1. A method for manufacturing a semiconductor devicecomprising: forming a semiconductor layer over a substrate in a filmformation unit; forming an oxide film on the semiconductor layer byapplying water in which ozone is dissolved while spinning the substratein the film formation unit; removing the oxide film and contaminantimpurities on the semiconductor layer in the film formation unit;forming a gate insulating film on and in direct contact with thesemiconductor layer; and forming a gate electrode on the gate insulatingfilm.
 2. The method for manufacturing a semiconductor device accordingto claim 1, wherein the oxide film and the contaminant impurities areremoved by applying a solution including fluorine.
 3. The method formanufacturing a semiconductor device according to claim 2, wherein thesolution including fluorine is one selected from the group consisting offluoric acid, dilute fluoric acid, ammonium fluoride, buffered fluoricacid, and mixed solution of fluoric acid and hydrogen peroxide.
 4. Themethod for manufacturing a semiconductor device according to claim 1,wherein the water comprises ozone at a concentration of 6 mg/L or more.5. The method for manufacturing a semiconductor device according toclaim 1, wherein the contaminant impurities comprise an element selectedfrom the group consisting of B, Na, K, Mg and Ca.
 6. The method formanufacturing a semiconductor device according to claim 1, wherein theoxide film is formed in an atmosphere including N₂.
 7. The method formanufacturing a semiconductor device according to claim 1, wherein thesemiconductor layer is a crystalline semiconductor layer.
 8. The methodfor manufacturing a semiconductor device according to claim 1, whereinthe semiconductor device is an active matrix liquid crystal displaydevice.
 9. The method for manufacturing a semiconductor device accordingto claim 1, wherein the semiconductor device is an Electro Luminescence(EL) display device.
 10. The method for manufacturing a semiconductordevice according to claim 1, wherein the gate insulating film is formedafter removing the oxide film and the contaminant impurities.
 11. Themethod for manufacturing a semiconductor device according to claim 1,wherein the step of removing the oxide film and the contaminantimpurities on the semiconductor layer is carried out while spinning thesubstrate.
 12. The method for manufacturing a semiconductor deviceaccording to claim 1, wherein the step of forming the gate insulatingfilm is carried out in the film formation unit.
 13. The method formanufacturing a semiconductor device according to claim 1, wherein thestep of forming the oxide film on the semiconductor layer and the stepof removing the oxide film and the contaminant impurities on thesemiconductor layer are carried out in a chamber purged with N₂.
 14. Amethod for manufacturing a semiconductor device comprising: forming asemiconductor layer over a substrate in a film formation unit; formingan oxide film on the semiconductor layer by applying water in whichozone is dissolved while spinning the substrate in a chamber in the filmformation unit; removing the oxide film and contaminant impurities onthe semiconductor layer in the chamber in the film formation unit;forming a gate insulating film on and in direct contact with thesemiconductor layer; and forming a gate electrode on the gate insulatingfilm.
 15. The method for manufacturing a semiconductor device accordingto claim 14, wherein the oxide film and the contaminant impurities areremoved by applying a solution including fluorine.
 16. The method formanufacturing a semiconductor device according to claim 15, wherein thesolution including fluorine is one selected from the group consisting offluoric acid, dilute fluoric acid, ammonium fluoride, buffered fluoricacid, and mixed solution of fluoric acid and hydrogen peroxide.
 17. Themethod for manufacturing a semiconductor device according to claim 14,wherein the water comprises ozone at a concentration of 6 mg/L or more.18. The method for manufacturing a semiconductor device according toclaim 14, wherein the contaminant impurities comprise an elementselected from the group consisting of B, Na, K, Mg and Ca.
 19. Themethod for manufacturing a semiconductor device according to claim 14,wherein the oxide film is formed in an atmosphere including N₂.
 20. Themethod for manufacturing a semiconductor device according to claim 14,wherein the semiconductor layer is a crystalline semiconductor layer.21. The method for manufacturing a semiconductor device according toclaim 14, wherein the semiconductor device is an active matrix liquidcrystal display device.
 22. The method for manufacturing a semiconductordevice according to claim 14, wherein the semiconductor device is anElectro Luminescence (EL) display device.
 23. The method formanufacturing a semiconductor device according to claim 14, wherein thegate insulating film is formed after removing the oxide film and thecontaminant impurities.
 24. The method for manufacturing a semiconductordevice according to claim 14, wherein the step of removing the oxidefilm and the contaminant impurities on the semiconductor layer iscarried out while spinning the substrate.
 25. The method formanufacturing a semiconductor device according to claim 14, wherein thestep of forming the gate insulating film is carried out in the filmformation unit.
 26. The method for manufacturing a semiconductor deviceaccording to claim 14, wherein the chamber is purged with N₂.
 27. Amethod for manufacturing a semiconductor device comprising: forming asemiconductor layer over a substrate; forming an oxide film on thesemiconductor layer by applying water in which ozone is dissolved whilespinning the substrate in a film formation unit; removing the oxide filmand contaminant impurities on the semiconductor layer in the filmformation unit; forming a gate insulating film on and in direct contactwith the semiconductor layer in the film formation unit; and forming agate electrode on the gate insulating film.
 28. The method formanufacturing a semiconductor device according to claim 27, wherein theoxide film and the contaminant impurities are removed by applying asolution including fluorine.
 29. The method for manufacturing asemiconductor device according to claim 28, wherein the solutionincluding fluorine is one selected from the group consisting of fluoricacid, dilute fluoric acid, ammonium fluoride, buffered fluoric acid, andmixed solution of fluoric acid and hydrogen peroxide.
 30. The method formanufacturing a semiconductor device according to claim 27, wherein thewater comprises ozone at a concentration of 6 mg/L or more.
 31. Themethod for manufacturing a semiconductor device according to claim 27,wherein the contaminant impurities comprise an element selected from thegroup consisting of B, Na, K, Mg and Ca.
 32. The method formanufacturing a semiconductor device according to claim 27, wherein theoxide film is formed in an atmosphere including N₂.
 33. The method formanufacturing a semiconductor device according to claim 27, wherein thesemiconductor layer is a crystalline semiconductor layer.
 34. The methodfor manufacturing a semiconductor device according to claim 27, whereinthe semiconductor device is an active matrix liquid crystal displaydevice.
 35. The method for manufacturing a semiconductor deviceaccording to claim 27, wherein the semiconductor device is an ElectroLuminescence (EL) display device.
 36. The method for manufacturing asemiconductor device according to claim 27, wherein the gate insulatingfilm is formed after removing the oxide film and the contaminantimpurities.
 37. The method for manufacturing a semiconductor deviceaccording to claim 27, wherein the step of removing the oxide film andthe contaminant impurities on the semiconductor layer is carried outwhile spinning the substrate.
 38. The method for manufacturing asemiconductor device according to claim 27, wherein the step of formingthe oxide film on the semiconductor layer and the step of removing theoxide film and the contaminant impurities on the semiconductor layer arecarried out in a chamber purged with N₂.